US4876310A - Hydrocarbon resin/polyphenylene ether comblike polymers, methods of producing these polymers, and their mixtures with polyphenylene ethers - Google Patents

Hydrocarbon resin/polyphenylene ether comblike polymers, methods of producing these polymers, and their mixtures with polyphenylene ethers Download PDF

Info

Publication number
US4876310A
US4876310A US06/834,423 US83442386A US4876310A US 4876310 A US4876310 A US 4876310A US 83442386 A US83442386 A US 83442386A US 4876310 A US4876310 A US 4876310A
Authority
US
United States
Prior art keywords
hydrocarbon resin
polyphenylene ether
unsaturated hydrocarbon
carbon
ethylene
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
US06/834,423
Other languages
English (en)
Inventor
Martin Bartmann
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Huels AG
Original Assignee
Huels AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Huels AG filed Critical Huels AG
Assigned to HULS AKTIENGESELLSCHAFT reassignment HULS AKTIENGESELLSCHAFT ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: BARTMANN, MARTIN
Application granted granted Critical
Publication of US4876310A publication Critical patent/US4876310A/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
    • C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
    • C08G65/44—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols by oxidation of phenols
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S525/00—Synthetic resins or natural rubbers -- part of the class 520 series
    • Y10S525/905—Polyphenylene oxide

Definitions

  • the present invention relates to novel hydrocarbon resin/polyphenylene ether comblike polymers, methods of preparing such polymers, and mixtures of these with polyphenylene ethers.
  • Polyphenylene ethers particularly poly(2,6-dimethylphenylene ether) (PPE), and methods for their preparation are known. See, for example, Buehler, "Special Plastics” (in German), pub. Akademieverlag, Berlin, 1978; and U.S. Pat. Nos. 3,306,874 and 3,306,875. And, for example, the preparation of PPEs by the oxidative coupling of ortho-substituted phenols mediated by copper-amine complexes in the presence of oxygen or oxygen-containing gas mixtures has proven itself to be an industrially feasible process.
  • Polyphenylene ethers are thermoplastics which are produced industrially in high volume. They are characterized by having high melting viscosities and high softening points. They are suitable for numerous technical applications requiring high heat deflection temperature. However, some properties of polyphenylene ethers are undesirable for certain technical applications. For example, molded parts made of polyphenylene ethers are excessively brittle because of their low impact strength. Processing these as melts has thus far not been industrially practicable to a great extent because the high temperatures required result in decomposition reactions which give the product an undesirable coloration.
  • polystyrene resins preferably rubber-modified high impact polystyrenes (HIPS).
  • HIPS high impact polystyrenes
  • German AS 19 32 234 and German OSs 24 34 848, 27 13 509 and 27 50 515 describe molding compounds comprised of styrene polymers, polyphenylene ethers and added compounds comprising differently structured hydrogenated or unhydrogenated block mixed polymers.
  • the latter are primarily polymerized vinylaromatic hydrocarbon blocks and polymerized conjugated diene polymer blocks.
  • German OS 21 07 935 describes a method for preparing a mixture from a polyphenylene ether and a rubber. According to this method, a 2,6-disubstituted phenol is polymerized in the presence of a rubber such as, e.g., polyisoprene. In this way a product is obtained in which the identities of the mixing components--the polyphenylene ether and the rubber--are retained. This is demonstrated in very clear fashion by the fact that the components of the mixture can be re-isolated by suitable measures. For example, the mixture can be first dissolved in a suitable solvent and then a separation can be carried out by addition of a second solvent which does not dissolve one of the two components. This is also applicable for fine-particle powder mixtures comprised of polyphenylene ethers and rubber, which mixtures are obtained according to German Pat. No. 21 11 043.
  • Polyphenylene ethers and hydrocarbon resins are only slightly compatible with each other.
  • addition of polyethylenes to polyphenylene ethers and to mixtures of polyphenylene ethers with polystyrene resins are limited to very small quantities of the added polyethylenes in order to prevent embrittlement and delamination (see European OS 0,080,666, p. 2, lines 4-10).
  • compatibility-promoting agents such as styrene-butadiene block copolymers.
  • 2,6-disubstituted phenols are oxidatively coupled in the presence of special manganese-amine catalysts, where the amino components are incorporated in the resulting polymer.
  • the functionalized polyphenylene ethers obtained can be grafted with unsaturated compounds at elevated temperatures (see European OS 0,101,873). This method is accompanied by the risk of producing insoluble gel-like materials--as documented in the Examples, infra. In any event, the grafting method described is not likely to be industrially practicable because it is applicable only to specially prepared functionalized polyphenylene ethers.
  • hydrocarbon resin component which is compatible with polyphenylene ethers.
  • the compatible component should be facile to prepare, and should not reduce the heat deflection temperature of the product, cause embrittlement or delamination, or cause unwanted discoloration (e.g., producing insoluble materials).
  • discoloration e.g., producing insoluble materials.
  • polyphenylene ether product containing such hydrocarbon resin.
  • the present inventors have now surprisingly found that all of the above objects are surprisingly satisfied with the discovery that functionalized hydrocarbon resins which are obtained from alkylated phenols and unsaturated hydrocarbon resins and having free phenol groups can be employed as co-monomers in the oxidative coupling of ortho-substituted phenols.
  • the resulting reaction product is made up of a mixture of a polyphenylene ether and a comblike polymer with a hydrocarbon resin as the main chain and polyphenylene ether groups as the side chain. This combination polymer can also be easily prepared separately.
  • the present invention thus provides a method for preparing polymers with recurring units of formula:
  • This method is characterized by using an oxidative coupling reaction of ortho-substituted phenols (Component I) in the presence of a 2,4,6-trisubstituted phenol (Component II) and a copper-amine catalyst.
  • a trisubstituted phenol component (Component II) containing a hydrocarbon resin with side groups of formulae ##STR2## is employed.
  • the groups R 5 , R 6 and R 7 are each independently a halogen atom, such as chlorine, bromine or iodine, a phenyl group, or an n-alkyl group with up to 6 carbon atoms, preferably a methyl group.
  • R 7 may alternatively be a hydrogen atom.
  • the present invention also provides novel hydrocarbon resin/polyphenylene ether comblike polymers and a novel mixture of a phenylene ether and a hydrocarbon resin polyphenylene either comblike polymer, both obtainable in accordance with the above method.
  • FIGS. 1 and 2 show the torsion oscillation spectra (indicating elasticity) for compressed plates produced in accordance with the present invention.
  • the present invention provides a method for preparing polymers having recurring units of formula:
  • Candidates for the substitued phenols include compounds of the general formula ##STR3## where R 1 and R 2 are independently a methyl group or a hydrogen atom, preferably hydrogen atom. R 3 and R 4 are a hydrogen atom and a tertiary alkyl group containing up to 6 C atoms, e.g., tertiary butyl, respectively. Alternatively R 3 and R 4 each may independently represent an n-alkyl group having up to 6 C atoms. Preferably 2,6-dimethylphenol is employed. Obviously, mixtures of these monomeric phenols may also be employed.
  • the trisubstituted phenol component (Component II) may be characterized by the formula:
  • A is derived from the basic framework of a hydrocarbon resin
  • B represents a phenolic side group of formula ##STR4##
  • the groups R 5 , R 6 and R 7 each represent a halogen atom, e.g., chlorine, bromine or iodine, a phenyl group, or an n-alkyl group having up to 6 C atoms, preferably a methyl group.
  • Group R 7 may also alternatively be a hydrogen atom.
  • n is the number of phenolic side groups bound to one molecule of the hydrocarbon resin. The average value of n is between 2 and 70, preferably between 5 and 30.
  • the modified hydrocarbon resins (Component II) of general formula A(B) n are obtained by reacting unsaturated hydrocarbon resins (Component III) with phenols (Component IV) of formula ##STR5## where R 5 , R 6 and R 7 have the same meanings as above (see Angew. Macromol. Chem., 24, 205 (1972) and 74, 17 (1978)).
  • R 5 and R 6 each represent a methyl group and R 7 represents a hydrogen atom.
  • Suitable acids include, e.g., sulfuric, perchloric, p-toluenesulfonic, methanesulfonic and benzenesulfonic. Methanesulfonic acid is preferred.
  • Suitable unsaturated hydrocarbon resins have a molecular weight of 1,000 to 1,000,000, preferably 50,000 to 500,000.
  • the double bonds of the hydrocarbon resin are not conjugated with each other. On average, the maximum number of double bonds should be 20 per 100 carbon-carbon bonds. As a rule there is at least one double bond.
  • Suitable such unsaturated hydrocarbon resins include terpolymers of ethylene, propylene, and some diene (such terpolymers are also called "EPDM" resins).
  • EPDM diene
  • a terpolymer of ethylene, propylene and ethylidenenorbornene is particularly suitable.
  • Polyalkenylenes obtained by ring-opening polymerization of a cyclic olefin with 5 to 12 C atoms, particularly polyoctenylenes, are also suitable.
  • the number n of added phenolic groups per molecule depends on, among other things, the molecular weight and the double bond content of the unsaturated hydrocarbon resin employed.
  • a mixture of the modified hydrocarbon resin (Component II) described immediately supra and the subsituted phenols (Component I) is subjected to the oxidative coupling reaction.
  • the amount of the modified hydrocarbon resin (Component II) in this mixture is between 1 and 50 wt.%, preferably between 3 and 20 wt.%.
  • Such a mixture can be prepared by simply combining the two components (Components I and II). It is also possible to react the unsaturated hydrocarbon resin (Component II) initially with an excess of phenol and then to directly subject the resulting reaction mixture to the oxidative coupling reaction.
  • this oxidative coupling reaction is carried out according to the method of German OSs 32 24 692 and 33 13 864 (U.S. patent application No. 4,429,106 and U.S. patent application No. 582,711, filed Feb. 23, 1984, now U.S. Pat. No. 4,537,948, respectively), and German patent application No. P 33 32 377.1 (U.S. patent application Ser. No. 632,125, filed July 18, 1984, now U.S. Pat. No. 4,659,803). These references are all hereby incorporated by reference.
  • the mixture is dissolved in a solvent which can dissolve both components.
  • solvents included toluene, benzene, ethylbenzene, xylene, chloroform, chlorobenzene or dichlorobenzene.
  • the preferred solvent is toluene.
  • An anti-solvent i.e., a precipitating agent which is a solvent in which the polyphenylene ether is insoluble but the comblike polymer is soluble, is added to this solution. Suitable anti-solvents are, e.g., hexane, heptane or cylcohexane. After the polyphenylene ether is separated out, the resulting solution is concentrated by evaporation to recover the comblike polymer.
  • Another possibility is to start with an organic solution of the reaction product obtained immediately after the oxidative coupling reaction.
  • a precondition for this is that the solvent chosen for the oxidative coupling reaction adequately dissolves the reaction product.
  • solvents may be identified from the relevant literature.
  • a particularly suitable such solvent is toluene.
  • the anti-solvent is then added, and the comblike polymer is isolated as described supra.
  • the comblike polymer itself, and mixtures of it with polyphenylene ethers, are of great interest for the preparation of molding compounds with novel properties.
  • Viscosities were determined with the aid of the J-value, analogously with DIN 53 728, by dissolving 0.5 g of the substance in 100 cc of chloroform.
  • DMP dimethylphenol
  • the mixture was allowed to react for four hours, cooled to 100° C., and then diluted with 50 kg of toluene. After cooling to room temperature, the solution was washed with water until neutral, and then dried over sodium sulfate.
  • the solution obtained in this fashion can be subjected directly to the oxidative coupling reaction for producing a mixture of poly(2,6-dimethyl-1,4-phenylene ether) and an EPDM resin/PPE comblike polymer.
  • Example 1 A mixture of 140 kg toluene, 26 kg methanol, 3.6 kg morpholine, and a solution of 0.2 kg CuCO 3 in 0.7 kg hydrobromic acid (48%) was charged into a vessel with a stirrer.
  • the polymer was precipitated by addition of methanol and dried.
  • M w (PPE/EPDM) ca. 400,000.
  • the polycondensation was interrupted by ceasing the air supply and simultaneously introducing a mixture of 45 kg water and 5 kg methanol, and instituting the passage of carbon dioxide at the rate of 5 m 3 hr -1 through the mixture. This gas flow was continued for 15 min. The phases were then separated, the organic phase was washed with 100 kg water at 80° C., followed by phase separation, and the product was then isolated by addition of 200 kg methanol, filtration and drying.
  • a modified polycotenylene was prepared, analogously to Example 3, from 2 kg polyoctenylene, 20 kg o-xylene, 1.6 kg 2,6-DMP, and a mixture comprised of 80 g methanesulfonic acid in 800 g o-xylene and 400 g 2,6-DMP.
  • the polyoctenylene had a J-value of 120 ml/g and trans-content of 80% (i.e., 80 wt.%.
  • Such a product is available commercially under the trade name Vestenamer® 8012 (manufacturer: Huels AG, postal zone D-4370 Marl 1, FRG). Additional characteristic parameters of this product may be found in the article Kautschuk, Kunststoffe 1981, pp.
  • the polyoctenylene may be prepared as well.
  • the reaction temperature was between 145° and 150° C.
  • the product was re-precipitated by first dissolving in toluene and then precipitating with methanol.
  • the modified polyoctenylene obtained according to Example 6 was polycondensed analogously to Example 4.
  • Compressed plates were produced from a mixture comprised of 90 wt.% of the polyphenylene ether obtained according to Example 2 without addition of the modified EPDM resin, and 10 wt.% of the EPDM resin employed in Example 1.
  • the torsion oscillation spectrum (to indicate elasticity) is given in FIG. 1. It is seen that above the glass transition temperature of the EPDM there is a marked reduction in the modulus of elasticity of the physical mixture.
  • Compressed plates were produced from a mixture of polyphenylene ether and an EPDM/polyphenylene ether comblike polymer obtained according to Example 2.
  • the torsion oscillation spectrum is given to FIG. 2. It is seen that even above the evident glass transition temperature of the EPDM phase the modulus of elasticity of the overall mixture remains substantially unchanged.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyethers (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
US06/834,423 1985-03-14 1986-02-28 Hydrocarbon resin/polyphenylene ether comblike polymers, methods of producing these polymers, and their mixtures with polyphenylene ethers Expired - Fee Related US4876310A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3509093 1985-03-14
DE19853509093 DE3509093A1 (de) 1985-03-14 1985-03-14 Kohlenwasserstoffharz-polyphenylenether-kammpolymere und deren mischungen mit polyphenylenethern sowie verfahren zu ihrer herstellung

Publications (1)

Publication Number Publication Date
US4876310A true US4876310A (en) 1989-10-24

Family

ID=6265152

Family Applications (1)

Application Number Title Priority Date Filing Date
US06/834,423 Expired - Fee Related US4876310A (en) 1985-03-14 1986-02-28 Hydrocarbon resin/polyphenylene ether comblike polymers, methods of producing these polymers, and their mixtures with polyphenylene ethers

Country Status (5)

Country Link
US (1) US4876310A (de)
EP (1) EP0195199B1 (de)
JP (1) JPS62526A (de)
AT (1) ATE43618T1 (de)
DE (2) DE3509093A1 (de)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5624027A (en) * 1995-05-10 1997-04-29 Joseph M. Torsella Apparatus for securing a computer diskette to an object
US20050154130A1 (en) * 2004-01-09 2005-07-14 Adeyinka Adedeji Method for the preparation of a poly(arylene ether)-polyolefin composition, and composition prepared thereby

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3658949A (en) * 1970-12-07 1972-04-25 Sumitomo Chemical Co Process for producing modified polyphenylene oxide composition
JPS529098A (en) * 1975-07-10 1977-01-24 Mitsubishi Gas Chem Co Inc Preparation of novel polyphenylene oxide modified with rubber
EP0101873A2 (de) * 1982-07-27 1984-03-07 General Electric Company Verfahren zur Modifizierung von ungesättigten Kautschuken und die hergestellten Gegenstände

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3658949A (en) * 1970-12-07 1972-04-25 Sumitomo Chemical Co Process for producing modified polyphenylene oxide composition
JPS529098A (en) * 1975-07-10 1977-01-24 Mitsubishi Gas Chem Co Inc Preparation of novel polyphenylene oxide modified with rubber
EP0101873A2 (de) * 1982-07-27 1984-03-07 General Electric Company Verfahren zur Modifizierung von ungesättigten Kautschuken und die hergestellten Gegenstände

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5624027A (en) * 1995-05-10 1997-04-29 Joseph M. Torsella Apparatus for securing a computer diskette to an object
US20050154130A1 (en) * 2004-01-09 2005-07-14 Adeyinka Adedeji Method for the preparation of a poly(arylene ether)-polyolefin composition, and composition prepared thereby
US7022765B2 (en) 2004-01-09 2006-04-04 General Electric Method for the preparation of a poly(arylene ether)-polyolefin composition, and composition prepared thereby
US20060079642A1 (en) * 2004-01-09 2006-04-13 Adeyinka Adedeji Method for the preparation of a poly (arylene ether)-polyolefin composition, and composition prepared thereby

Also Published As

Publication number Publication date
DE3509093A1 (de) 1986-09-18
DE3663674D1 (en) 1989-07-06
JPS62526A (ja) 1987-01-06
EP0195199A1 (de) 1986-09-24
EP0195199B1 (de) 1989-05-31
ATE43618T1 (de) 1989-06-15

Similar Documents

Publication Publication Date Title
US5880221A (en) Redistribution of polyphenylene ethers and polyphenylene ethers with novel structure
US6339131B1 (en) Synthesis of poly (arylene ether)-poly(organosiloxane) copolymers
US5122578A (en) Polyphenylene ether-polyarylene sulfide compositions
EP0282664A1 (de) Schlagzähe Polyamidharz-Zusammensetzung und Verfahren zu deren Herstellung
US4824915A (en) Functionalized polyphenylene ethers and blends with polyamides
US3663661A (en) Rubber modified polyphenylene ether and process
US3976725A (en) High impact strength thermoplastic compositions
US4153644A (en) Resin composition containing polyphenylene oxide
US4876310A (en) Hydrocarbon resin/polyphenylene ether comblike polymers, methods of producing these polymers, and their mixtures with polyphenylene ethers
US5336732A (en) Process for forming polyamide/poly(phenylene ether) blends
US4948838A (en) Thermoplastic molding materials
US4778849A (en) Thermoplastic molding compositions based on polyphenylene ether and an impact strength improving comblike polymer
JPS63503388A (ja) エポキシドで官能化されたポリフェニレンエーテルおよび製造方法
JPH05500535A (ja) ジカルボキシレートでキャッピングされたポリフェニレンエーテルからのポリフェニレンエーテル―ポリアリ―レンスルフィド組成物
US4118348A (en) Method for preparing blends of rubber, a polyphenylene ether resin and an alkenyl aromatic addition polymer
US4073765A (en) Filled polyphenylene ether compositions having improved toughness
US5084551A (en) Polyphenylene ether process and resin composition
CA1058349A (en) Thermoplastic molding compositions of a polyphenylene ether resin and interpolymers of an alkenyl aromatic compound and a block copolymer
JP2557637B2 (ja) 耐衝撃性ポリアミド樹脂組成物およびその製法
CA1117692A (en) Process for the preparation of polyphenylene oxide compositions
Hay Chemical modification of poly (phenylene oxide) s
JPH05117387A (ja) ヒドロキシル化ポリフエニレンエーテルの製造方法
US20070100091A1 (en) Crosslinked poly(arylene ether) composition, method, and article
JPH06200015A (ja) アルコキシシリル化ポリフェニレンエーテルの製造方法
CA1269778A (en) Impact-resistant polyamide resin composition and process for producing the same

Legal Events

Date Code Title Description
AS Assignment

Owner name: HULS AKTIENGESELLSCHAFT, GERMANY

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:BARTMANN, MARTIN;REEL/FRAME:005134/0472

Effective date: 19890524

REMI Maintenance fee reminder mailed
LAPS Lapse for failure to pay maintenance fees
FP Lapsed due to failure to pay maintenance fee

Effective date: 19931024

STCH Information on status: patent discontinuation

Free format text: PATENT EXPIRED DUE TO NONPAYMENT OF MAINTENANCE FEES UNDER 37 CFR 1.362